Water-soluble disazo compounds, having a fiber-reactive group of the vinylsulfone series, suitable as dyestuffs

ABSTRACT

Water-soluble disazo compounds, processes for their preparation of their use as dyestuffs 
     Disazo compounds of the general formula (1) defined below, ##STR1## which have fiber-reactive properties and are suitable as useful dyestuffs for dyeing material containing carboxamide groups and/or material containing hydroxy groups, such as fiber material, for example wool and cellulose fiber materials, are described. 
     In formulas (1): 
     D* is phenylene, which can be substituted by 1 or 2 substituents from the group comprising lower alkyl, lower alkoxy, chlorine, bromine, sulfo and carboxy, or is a naphthylene which is optionally substituted by sulfo; 
     D is the meta- or para-phenylene radical; 
     A is a direct bond or the methylene group or the group --N(R)--, where R has the meaning given below; 
     R is lower alkyl, which can be substituted; 
     Y 1  and Y`each denote the vinyl group or the 62 -chloroethyl or β-sulfatoethyl group and 
     M is a hydrogen atom or an alkali metal.

This application is a continuation of copending application Ser. No.07/470,085, filed on Jan. 25, 1990, now abandoned.

German Patent No. 1,262,213 discloses, in Example 9, a navy blue disazodyestuff having 1-amino-8-naphthol-3,6-disulfonic acid as the bivalentcoupling component and two aniline diazo components, the diazocomponents both possessing a β-sulfatoethyl-sulfonamide group as thefiber-reactive grouping. A dyestuff of the same structure but containingthe N-methyl-N-(β-sulfatoethyl-sulfonyl)-amide group, and thevinylsulfonamide derivative thereof are known from Example 11 of GermanAuslegeschrift No. 1,235,257 and U.S. Pat. No. 3,334,961. Dyestuffs ofsimilar structure are known from Examples 7 and 8 of European PatentApplication Publication No. 0,219,080 A.

Improved navy blue disazo compounds which have fiber-reactive dyestuffproperties, exhibit a constant color yield when used in exhaustiondyeing processes at dyeing temperatures between 40° and 80° C. and areparticularly suitable for use in pad dyeing processes, in which theyalready have a high color yield and a high degree of fixing at roomtemperature, have now been found with the present invention. Thesecompounds are also particularly suitable for use in the one-phaseprinting process because of their stability in alkaline printing pastesand their high color yield.

The disazo compounds according to the invention correspond to thegeneral formula (1) ##STR2## in which: D* is a phenylene radical,preferably a meta- or para-phenylene radical, which can be substitutedby 1 or 2 substituents from the group comprising alkyl having 1 to 4carbon atoms, such as ethyl or in particular methyl, alkoxy having 1 to4 carbon atoms, such as ethoxy or in particular methoxy, chlorine,bromine, sulfo or carboxy, or is a naphthylene radical, which can besubstituted by 1 or 2 sulfo groups;

D is the meta- or para-phenylene radical;

A is a direct bond or the methylene group or a bivalent amino group ofthe formula --N(R)-- where R has one of the meanings given below;

R is an alkyl group having 1 to 4 carbon atoms, such as the ethyl or inparticular the methyl group, which can be substituted, for example by acyano or a carbalkoxy group having 2 to 5 carbon atoms, such as thecarbomethoxy or carbethoxy group, for example the β-cyanoethyl orβ-carbomethoxyethyl group;

Y¹ and Y² each denote the vinyl group or the β-chloroethyl orβ-sulfatoethyl group, it being possible for Y¹ and Y² to have meaningswhich are identical to or different from one another; and

M is a hydrogen atom or an alkali metal, such as lithium, potassium orsodium.

Disazo compounds according to the invention are accordingly also thosewhich correspond to the general formulae (1a) and (1b) ##STR3## in whichM, D*, D, A, R, Y¹ and Y² have the abovementioned particularly preferredmeanings.

The individual formula members of the general formulae (1) can beidentical to or different from one another within their meanings. D* ispreferably a meta- or para-phenylene radical, which can be substitutedby 1 or 2 substituents chosen from the following group of substitutents:2 methoxy, 1 ethoxy, 1 methyl, 2 chloro and 1 sulfo. Particularlypreferably, D* is the p-phenylene radical and A is a direct bond. D* isfurthermore preferably a naphthylene radical, in the 2-position of whichthe azo group is bonded and which can be substituted by a sulfo group,in addition to the grouping --A--SO₂ --Y¹.

Preferably, both Y¹ and Y² represent a β-sulfatoethyl group.

The substituents "sulfo", "carboxy" and "sulfato" include both the acidform thereof and the salt form thereof. Sulfo groups accordingly denotegroups corresponding to the general formula --SO₃ M, carboxy groupsdenote groups corresponding to the general formula --COOM and sulfatogroups correspondingly denote groups of the general formula --OSO₃ M, ineach case where M has the abovementioned meaning.

The novel compounds of the general formula (1) can be present in acidform. They are preferably in the form of their alkali metal salts andare preferably used in the form of the alkali metal salts for dyeing(including printing) fiber materials containing hydroxy groups and fibermaterials containing carboxamide groups.

The present invention furthermore relates to a process for thepreparation of the disazo compounds according to the invention, whichcomprises coupling the diazonium compounds of the amines of the generalformulae (2) and (3) ##STR4## in which D*, D, A, R, Y¹ and Y² have theabovementioned meanings, with 1-amino-3,6- or -4,6-disulfo-8-naphthol asthe bivalent coupling component in any desired sequence, the firstcoupling reaction being carried out in a strongly acid aqueous medium,such as at a pH between 0 and 2, preferably between 1 and 1.5, and thesecond coupling reaction being carried out in a weakly acid to weaklyalkaline aqueous medium, such as at a pH between 4 and 8, preferablybetween 4.5 and 7. The coupling temperature is as a rule between 0° and30° C., preferably between 10° and 20° C.

Examples of aromatic amines of the general formula (2) are4-[N-methyl-N-(β-sulfatoethylsulfonyl)]-amino-aniline,3-[N-methyl-N-(β-sulfatoethylsulfonyl)]-aminoaniline,6-sulfo-4-[N-methyl-N-(β-sulfatoethylsulfonyl)]-amino-aniline,6-sulfo-3-[N-methyl-N-(β-sulfatoethylsulfonyl)]-amino-aniline,4-[N-ethyl-N-(β-sulfatoethylsulfonyl)]-amino-aniline,3-[N-ethyl-N-(β-sulfatoethylsulfonyl)]-amino-aniline,4-chloro-3-[N-ethyl-N-(β-sulfatoethylsulfonyl)]-amino-aniline,4-methoxy-3-[N-ethyl-N-(β-sulfatoethylsulfonyl)]-amino-aniline,2-chloro-5-[N-ethyl-N-(β-sulfatoethylsulfonyl)]-amino-aniline,2-trifluoromethyl-4-[N-ethyl-N-(β-sulfatoethylsulfonyl)]-amino-aniline,3-methoxy-4-[N-methyl-N-(β-sulfatoethylsulfonyl)]-aniline,2,5-dimethoxy-4-[N-methyl-N-(β-sulfatoethylsulfonyl)]-aniline,3-[N-(β-cyanoethyl)-N-(β'-sulfatoethylsulfonyl)]-amino-aniline,4-[N-(β-cyanoethyl)-N-(β'-sulfatoethylsulfonyl)]-amino-aniline,4-chloro-3-[N-methyl-N-(β'-sulfatoethylsulfonyl)]-amino-aniline,3-chloro-4-[N-methyl-N-(β'-sulfatoethylsulfonyl)]-amino-aniline,4-methoxy-3-[N-methyl-N-(β-sulfatoethylsulfonyl)]-amino-aniline,2-methoxy-3-[N-methyl-N-(β-sulfatoethylsulfonyl)]-amino-aniline,4,6-dimethyl-3-[N-methyl-N-(β-sulfatoethylsulfonyl)]-amino-aniline,2-chloro-5-[N-methyl-N-(β-sulfatoethylsulfonyl)]-amino-aniline,4-(β-sulfatoethylsulfonyl)-aniline,6-sulfo-4-(β-sulfatoethylsulfonyl)-aniline, 4-vinylsulfonyl-aniline,3-(β-sulfatoethylsulfonyl)-aniline,3-sulfo-4-(β-sulfatoethylsulfonyl)-aniline, 3-vinylsulfonyl-aniline,2-methoxy-5-(β-sulfatoethylsulfonyl)-aniline,2-methoxy-5-vinylsulfonyl-aniline,4-methoxy-5-(β-sulfatoethylsulfonyl)-aniline,2-methoxy-4-(β-sulfatoethylsulfonyl)-aniline,2,5-dimethoxy-4-(β-sulfatoethylsulfonyl)-aniline,2,5-dimethoxy-4-vinylsulfonyl-aniline,2,4-dimethoxy-5-(β-sulfatoethylsulfonyl)-aniline,2-methoxy-5-methyl-4-(β-sulfatoethylsulfonyl)-aniline,2-methoxy-5-methyl-4-vinylsulfonyl,2-methoxy-5-chloro-4-(β-sulfatoethylsulfonyl)-aniline,2-chloro-5-(β-sulfatoethylsulfonyl)-aniline,2,6-dichloro-4-(β-sulfatoethylsulfonyl)-aniline,2-bromo-4-(β-sulfatoethylsulfonyl)-aniline,2-carboxy-5-(β-sulfatoethylsulfonyl)-aniline,2-sulfo-4-(β-sulfatoethylsulfonyl)-aniline,4-(β-sulfatoethylsulfonyl)-1-amino-naphthalene,5-(β-sulfatoethylsulfonyl)-1-amino-naphthalene,6-(β-sulfatoethylsulfonyl)-sulfatoethylsulfonyl)-2-amino-naphthalene,7-(β-sulfatoethylsulfonyl)-2-amino-naphthalene,8-(β-sulfatoethylsulfonyl)-2-amino-naphthalene,6-(β-sulfatoethylsulfonyl)-1-sulfo-2-amino-naphthalene,8-(β-sulfatoethylsulfonyl)-6-sulfo-2-amino-naphthalene,6-(β-sulfatoethylsulfonyl)-8-sulfo-2-amino-naphthalene,3-(β-sulfatoethylsulfonyl-methyl)-aniline and4-(β-sulfatoethylsulfonyl-methyl)-aniline.

Examples of aromatic amines of the general formula (3) are4-[N-methyl-N-(β-sulfatoethylsulfonyl)]-amino-aniline,3-[N-methyl-N-(β-sulfatoethylsulfonyl)]-amino-aniline,4-(N-methyl-N-vinylsulfonyl)-amino-aniline,3-(N-methyl-N-vinylsulfonyl)-amino-aniline,4-[N-ethyl-N-(β-sulfatoethylsulfonyl)]-amino-aniline,3-[N-ethyl-N-(β-sulfatoethylsulfonyl)]-amino-aniline,4-[N-(β-cyanoethyl)-N-(β'-sulfatoethylsulfonyl)]-amino-aniline,3-[N-(β-cyanoethyl)-N-(β'-sulfatoethylsulfonyl)]-amino-aniline,4-[N-(β-carbomethoxy-ethyl)-N-(β'-sulfatoethylsulfonyl)]-amino-anilineand3-[N-(β-carbomethoxy-ethyl)-N-(β'-sulfatoethylsulfonyl)]-amino-aniline.

The compounds according to the invention can be isolated from theirpreparation mixtures by generally known methods for water-solublecompounds, thus, for example, by precipitation from the reaction mediumby means of an electrolyte, such as, for example, sodium chloride orpotassium chloride, or by evaporation of the reaction solution itself,for example by spray drying.

If the last type of isolation mentioned is chosen for the compoundsaccording to the invention, in cases where the reaction solutioncontains relatively large amounts of sulfate it is advisable for thesulfate present in the solutions to be removed, for example byprecipitation as calcium sulfate and removal by filtration, before theevaporation. In some cases, it may also be desirable to put the dyestuffsolution to use directly for dyeing as a liquid preparation, ifappropriate after concentration and/or addition of buffer substances.

The novel compounds of the present invention are outstandingly suitableas dyestuffs, in particular as fiber-reactive dyestuffs, for dyeing orprinting materials of fibers containing hydroxy and/or carboxamidegroups, such as, in particular, of natural or regenerated cellulose orof naturally occurring, regenerated or synthetic polyamides orpolyurethanes, such as, for example, cotton, hemp, linen, jute, filamentviscose, wool, silk, polyamide-6, polyamide-6,6, polyamide-11 orpolyamide-4. The novel compounds are particularly suitable for dyeingand printing cellulose fiber materials.

The novel compounds are applied to and fixed on the substrates mentionedby dyeing and printing processes analogous to those which are known andcustomary for water-soluble, in particular fiber-reactive, dyestuffs.They have a good to very good solubility and stability in the printingpastes and dyebaths, exhibit a high tinctorial strength and a good colorbuild-up and produce, with high degrees of fixing, navy blue to blackdyeings and prints which, especially in the case of dyeings and printson cellulose fibers, are distinguished by good to very good fastnessproperties during use and fabrication, such as, for example, fastnessesto light, washing, seawater, chlorinated water, acid and alkali,fastnesses to cross-dyeing, fastnesses to alkaline and acidperspiration, fastnesses to exhaust gases (fastness to nitric oxide) andfastnesses to ironing, pleating, decatizing, dry cleaning and rubbing.Non-fixed portions of dyestuff can easily be washed out. The dyeings andprints of the compounds according to the invention also have a goodstability towards copper ions and towards substances which donate copperions. When compounds according to the invention are used for printingcellulose fiber materials, hardening of the handle of the dyed materialis moreover avoided; sharp contours with a clear white background arefurthermore obtained by printing. The dyeings and prints produced withthe compounds according to the invention do not stain when laid down andplaited down in the non-fixed state and do not bleed and have a highresistance to acid storage, and thus exhibit no "acid fading".

However, the very good fastnesses to light in the wet and dry state areto be particularly emphasized. Very good wet light-fastnesses are foundon exposure to light of dyeings and prints which have been impregnatedwith distilled water, with drinking water and with alkaline and acidperspiration solutions. These wet light-fastnesses have since acquired ahigh practical value.

The present invention furthermore relates to the use of the compoundsaccording to the invention for dyeing or printing the abovementionedfiber materials and to a process for dyeing or printing theabovementioned fiber materials in which the compounds according to theinvention are applied to and then fixed on the fiber material byprocedures which are analogous to those which are known and customary inthe dyeing and printing industry. For example, these processes arecarried out by treating cellulose fiber materials in an aqueous dyebath,which contains customary dyeing auxiliaries if appropriate, by theexhaustion process using alkaline agents, that is to say at atemperature between 15° and 105° C. and preferably between 40° and 80°C., the fiber material being dyed in very good color yields.

In particular, the dyeing temperature has only little influence on thevery high degree of fixing in the temperature range between 40° and 80°C.; this results in a dyeing with a uniformly very good color yield,which is essentially independent of the dyeing temperature chosen withinthis temperature range.

Dyeings with excellent color yields are likewise obtained on cellulosefiber materials in particular by means of the padding processes whichare known and customary in the art; this process can be carried out as aone- or two-phase process, so that fixing can be carried out with theaid of the alkaline agent which has been applied to the fiber materialat the same time as or subsequently to the application of the dyestuff,or by batching of the padded fiber material for 5 minutes to 20 hours atroom temperature or temperatures up to 60° C., or by steaming or bytreatment with dry heat. Non-fixed portions of dyestuff can easily bewashed out.

The compounds according to the invention are used in printing processesby methods which are analogous to the printing and fixing methods whichare known and customary for dyeing cellulose fibers. The procedurepreferably followed here is in one phase, using a printing pastecontaining the compound according to the invention and sodium carbonateor another acid-binding agent, such as potassium bicarbonate, sodium orpotassium carbonate, sodium hydroxide solution, potassium hydroxidesolution or sodium trichloroacetate, with subsequent steaming of theprinted material at 101° to 103° C., or in two phases, by printing witha neutral or weakly acid printing paste containing the compoundaccording to the invention and subsequent fixing by means of a hotelectrolyte-containing alkaline bath, or by overpadding with analkaline, electrolyte-containing liquor and subsequent batching,steaming or dry heat treatment of the overpadded material; deep printswith a good contour status and a clear white background are obtained.The prints exhibit a high constancy of shade, regardless of the fixingconditions.

Dyeing of the polyamide or polyurethane fibers is usually carried outfrom an acid medium. Thus, for example, acetic acid or a buffer ofacetic acid and ammonium acetate can be added to the dyebath in order toobtain the desired pH. An addition of customary leveling auxiliaries,for example based on a reaction product of cyanuric chloride with threetimes the molar amount of an aminobenzenesulfonic acid and/or anaminonaphthalenesulfonic acid or based on a reaction product ofstearylamine with ethylene oxide, is recommended for the purpose ofachieving a useful levelness of the dyeings. The dyeings can be producedeither at the boiling point or at 110° to 120° C.

The following Examples serve to illustrate the invention. The partsmentioned therein are parts by weight and the percentage data representpercentages by weight, unless noted otherwise. Parts by weight bear thesame relationship to parts by volume as the kilogram to the liter.

The compounds described by way of their formulae in the Examples areshown in the form of the free acids; they are in general prepared andisolated in the form of their sodium or potassium salts and used fordyeing in the form of their salts. The starting compounds and componentsmentioned in the form of the free acid in the following Examples, inparticular the Tabular Examples, can likewise be employed in thesynthesis as such or in the form of their salts, preferably alkali metalsalts.

The absorption maxima (λ_(max)) in the visible range stated for thecompounds according to the invention were determined with the aid of thealkali metal salts thereof in aqueous solution. In the Tabular Examples,the λ_(max) values are given in parentheses where the color shade isstated; the wavelength stated relates to nm.

EXAMPLE 1

31.9 parts of 1-amino-8-naphthol-3,6-dislulfonic acid are added to anaqueous diazonium salt solution of 4-(β-sulfatoethylsulfonyl)-aniline,prepared in the customary manner by diazotization of 28.1 parts of thisaniline by means of 30 parts of concentrated hydrochloric acid, 20 partsby volume of an aqueous 5N sodium nitrite solution and 200 parts ofwater at 0 ° to 5° C., and the coupling reaction is brought tocompletion at a pH of 0.8 to 2 and a temperature of about 10° C., whilestirring for several hours.

An aqueous diazonium salt suspension, prepared in an analogous manner tothe first diazonium salt, of 30.9 parts of4-[N-methyl-N-(β-sulfatoethylsulfonyl)]-amino-aniline is added to thissynthesis mixture containing the monoazo intermediate compound prepared.The second coupling reaction is carried out at a pH of 6 to 7 and atemperature of 10° to 20° C.

The synthesis solution is then clarified by the customary route, forexample by filtration, after addition of kieselguhr, and the disazocompound according to the invention is isolated, for example byevaporation or spray drying. The alkali metal salt (sodium salt)according to the invention of the compound of the formula ##STR5## isobtained in the form of a black electrolyte-containing powder. Thedisazo compound according to the invention has very good fiber-reactivedyestuff properties and dyes the fiber materials mentioned in thedescription, such as, in particular, cellulose fiber materials, forexample cotton, in navy blue shades by the application and fixingmethods customary in the art. The disazo compound according to theinvention is also particularly suitable for use in pad dyeing processesat room temperature. The dyeings and prints obtainable with it exhibitgood fastnesses during use and fabrication, of which the goodlight-fastnesses of the dyeings and prints in both the dry state and thestate moistened with drinking water or with an aqueous perspirationsolution and moreover the fastnesses to chlorine, washing andperspiration may be singled out in particular.

EXAMPLE 2

The disazo compound of Example 1 according to the invention can also beprepared in an equally good quality by adding the equivalent amount of1-amino-8-naphthol-3,6-disulfonic acid, as the coupling component, to anequimolar mixture of the two diazonium salts in an aqueous medium,obtainable, for example, by simultaneous diazotization of the twostarting amines, and initially keeping the batch at a pH of 0.8 to 1.5and a temperature of 8° to 10° C. for several hours and then increasingthe pH to 6 to 7 and allowing the reaction temperature to rise to 20° to30° C. The second coupling reaction has then gone to completion after 2to 3 hours. The disazo compound according to the invention is isolatedin accordance with Example 1.

EXAMPLE 3

58 parts of the monoazo compound1-amino-3,6-disulfo-2-[4'-(β-sulfatoethylsulfonyl-phenyl)]-azo-8-naphtholare added to an aqueous diazonium salt suspension of 30.9 parts of4-[N-methyl-N-(β-sulfatoethylsulfonyl)]-amino-aniline and the couplingreaction is carried out at 10° to 30° C. and a pH of 6 to 7.

The disazo compound according to the invention is isolated in thecustomary manner. It is identical to that of Example 1 and exhibits thesame dyestuff properties.

EXAMPLE 4

30.9 parts of 4-[N-methyl-N-(β-sulfatoethylsulfonyl)]-amino-aniline arediazotized in an aqueous medium in the customary manner, 31.9 parts of1-amino-8-naphthol-3,6-disulfonic acid are added to the resultingdiazonium salt suspension and the coupling reaction is brought tocompletion at a temperature of 10° C. and a pH of 1.5 to 2.5 in thecourse of about 24 hours.

The second coupling reaction is carried out with the diazonium salt of28.1 parts of 4-(β-sulfatoethylsulfonyl)-aniline at a pH between 6 and 7and a temperature between 15° and 25° C.

The disazo compound according to the invention is isolated in thecustomary manner and is obtained in the form of its alkali metal salt,such as the sodium salt. It has the formula, written in the form of thefree acid, ##STR6## and exhibits very good fiber-reactive dyestuffproperties. On cellulose fiber materials in particular, it produces, bythe customary application and fixing processes for fiber-reactivedyestuffs, navy blue dyeings and prints with good fastnesses duringfabrication and use.

EXAMPLE 5

The diazonium salt of 30.9 parts of3-[N-methyl-N-(β-sulfatoethylsulfonyl)]-amino-aniline-6-sulfonic acid iscoupled with 58 parts of the monoazo compound1-amino-3,6-disulfo-2-[4'-(β-sulfatoethylsulfonyl-phenyl)]-azo-8-naphtholin an aqueous medium at a pH between 6 and 7 and a temperature between10° and 30° C. The disazo compound according to the invention of theformula ##STR7## is obtained in the form of the alkali metal salt. Ithas very good fiber-reactive dyestuff properties and dyes, for example,cellulose fibers in navy blue shades in high fixing quotas and with goodfastnesses during use and fabrication, such as, in particular, with thefastnesses mentioned for the disazo compound of Example 1 according tothe invention.

EXAMPLE 6

61.8 parts of 4-[N-methyl-N-(β-sulfatoethylsulfonyl)]-amino-aniline,dissolved in 500 parts of water and 65 parts of aqueous concentratedhydrochloric acid, are diazotized at 5° to 10° C. by addition of aconcentrated aqueous solution of 14 parts of sodium nitrite. The batchis brought to a pH of 2.5 and 60.6 parts of1-amino-8-naphthol-3,6-disulfonic acid are added. The first couplingreaction is carried out at a pH of 1.5 to 2 and a temperature of about10° C. for about 20 hours, and the second coupling reaction is thencarried out at a pH of 7 and a temperature of about 20° C.

After clarification of the synthesis solution, the disazo compoundaccording to the invention is isolated by spray drying. It has theformula, written in the form of the free acid, ##STR8## It exhibits verygood fiber-reactive dyestuff properties and produces, by the customarydyeing process, the exhaustion and padding process and printingprocesses for fiber-reactive dyestuffs, in particular on cellulose fibermaterials, greenish-tinged navy blue dyeings and prints with goodfastness properties in a very high color yield and with a very highdegree of fixing. Of the fastness properties, those which are alsomentioned for the disazo compound according to the invention and ofExample 1 may be singled out in particular.

Examples 7 to 82

The following Tabular Examples contain further disazo compoundsaccording to the invention corresponding to a general formula (A)##STR9## with the aid of their components, that is to say the diazoradical D¹ as the radical of the first diazo component D¹ --NH₂ whichcan be coupled under strongly acid conditions, the radical D², as thesecond diazo component D² --NH₂ which can be coupled under weakly acidto neutral conditions, and the bivalent coupling component1-amino-8-naphthol-3,6- or -4,6-disulfonic acid. They can be prepared inthe manner according to the invention, for example analogously to one ofthe above Embodiment examples with the aid of the starting compoundswhich can be seen from the particular Tabular Example (the 1st diazocomponent D¹ --NH₂, the 2nd diazo component D² --NH₂ and thecorresponding bivalent coupling component). They have very goodfiber-reactive dyestuff properties and produce, in particular oncellulose fiber materials by the application and fixing methodscustomary for fiber-reactive dyestuffs, deep, navy blue dyeings andprints with good fastness properties.

    __________________________________________________________________________    Disazo compound of the formula (A)                                                                 Position of                                                                   the group                                                Example                                                                            Radical D.sup.2 --SO.sub.3 H                                                                        Radical D.sup.1                                                                              Color shade                         __________________________________________________________________________     7   3-[N-methyl-N-(β-sulfatoethyl-                                                           3-    4-(β-sulfatoethyl-                                                                      navy                                     sulfonyl)]-amino-phenyl                                                                             sulfonyl)-phenyl                                                                             blue (600)                           8   3-[N-ethyl-N-(β-sulfatoethyl-                                                            3-    4-(β-sulfatoethyl-                                                                      navy                                     sulfonyl)]-amino-phenyl                                                                             sulfonyl)-phenyl                                                                             blue (600)                           9   3-[N-(β-cyanoethyl)-(β-sulfato-                                                     3-    4-(β-sulfatoethyl-                                                                      navy                                     ethylsulfonyl)]-amino-phenyl                                                                        sulfonyl)-phenyl                                                                             blue (602)                          10   4-(N-methyl-N-vinylsulfonyl)-                                                                 3-    4-(β-sulfatoethyl-                                                                      navy                                     amino-phenyl          sulfonyl)-phenyl                                                                             blue (610)                          11   3-(N-methyl-N-vinylsulfonyl)-                                                                 3-    4-(β-sulfatoethyl-                                                                      navy                                     amino-phenyl          sulfonyl)-phenyl                                                                             blue (600)                          12   3-(N-methyl-N-vinylsulfonyl)-                                                                 3-    4-vinylsulfonyl-phenyl                                                                       navy                                     amino-phenyl                         blue (600)                          13   4-(N-methyl-N-vinylsulfonyl)-                                                                 3-    4-vinylsulfonyl-phenyl                                                                       navy                                     amino-phenyl                         blue (609)                          14   4-(N-methyl-N-vinylsulfonyl)-                                                                 3-    2-sulfo-4-(β-sulfatoethyl-                                                              navy                                     amino-phenyl          sulfonyl)-phenyl                                                                             blue (596)                          15   3-(N-methyl-N-vinylsulfonyl)-                                                                 3-    2-sulfo-4-(β-sulfatoethyl-                                                              navy                                     amino-phenyl          sulfonyl)-phenyl                                                                             blue (590)                          16   4-[N-methyl-N-(β-sulfatoethyl-                                                           3-    2-sulfo-4-(β-sulfatoethyl-                                                              navy                                     sulfonyl)]-amino-phenyl                                                                             sulfonyl)-phenyl                                                                             blue (597)                          17   3-[N-methyl-N-(β-sulfatoethyl-                                                           3-    2-sulfo-4-(β-sulfatoethyl-                                                              navy                                     sulfonyl)]-amino-phenyl                                                                             sulfonyl)-phenyl                                                                             blue                                18   3-[N-methyl-N-(β-sulfatoethyl-                                                           3-    2-sulfo-5-(β -sulfatoethyl-                                                             navy                                     sulfonyl)]-amino-phenyl                                                                             sulfonyl)-phenyl                                                                             blue (594)                          19   4-[N-methyl-N-(β-sulfatoethyl-                                                           3-    2-sulfo-5-(β-sulfatoethyl-                                                              navy                                     sulfonyl)]-amino-phenyl                                                                             sulfonyl)-phenyl                                                                             blue                                20   3-[N-methyl-N-(vinylsulfonyl)]-                                                               3-    2-sulfo-5-(β-sulfatoethyl-                                                              navy                                     amino-phenyl          sulfonyl)-phenyl                                                                             blue (596)                          21   4-[N-methyl-N-(vinylsulfonyl)]-                                                               3-    2-sulfo-5-(β-sulfatoethyl-                                                              navy                                     amino-phenyl          sulfonyl)-phenyl                                                                             blue (598)                          22   4-[N-methyl-N-(vinylsulfonyl)]-                                                               3-    2,5-dimethoxy-4-(β-sulfato-                                                             navy                                     amino-phenyl          ethylsulfonyl)-phenyl                                                                        blue                                23   4-[N-methyl-N-(β-sulfatoethyl-                                                           3-    2,5-dimethoxy-4-(β-sulfato-                                                             navy                                     sulfonyl)]-amino-phenyl                                                                             ethylsulfonyl)-phenyl                                                                        blue (520)                          24   3-[N-methyl-N-(β-sulfatoethyl-                                                           3-    2,5-dimethoxy-4-(β-sulfato-                                                             navy                                     sulfonyl)]-amino-phenyl                                                                             ethylsulfonyl)-phenyl                                                                        blue                                25   3-(N-ethyl-N-vinylsulfonyl)-                                                                  3-    2,5-dimethoxy-4-(β-sulfato-                                                             navy                                     amino-phenyl          ethylsulfonyl)-phenyl                                                                        blue                                26   3-(N-ethyl-N-vinylsulfonyl)-                                                                  3-    2-methoxy-5-methyl-4-(β-                                                                navy                                     amino-phenyl          sulfatoethylsulfonyl)-phenyl                                                                 blue                                27   4-[N-methyl-N-(β-sulfatoethyl-                                                           3-    2-methoxy-5-methyl-4-(β-                                                                navy                                     sulfonyl)]-amino-phenyl                                                                             sulfatoethylsulfonyl)-phenyl                                                                 blue (506)                          28   4-[N-methyl-N-(β-sulfatoethyl-                                                           3-    6-(β-sulfatoethylsulfonyl)-                                                             navy                                     sulfonyl)]-amino-phenyl                                                                             naphth-2-yl    blue (512)                          29   3-[N-methyl-N-(β-sulfatoethyl-                                                           3-    6-(β-sulfatoethylsulfonyl)-                                                             navy                                     sulfonyl)]-amino-phenyl                                                                             naphth-2-yl    blue                                30   3-[N-methyl-N-(β-sulfatoethyl-                                                           3-    6-(β-sulfatoethylsulfonyl)-                                                             navy                                     sulfonyl)]-amino-phenyl                                                                             1-sulfo-naphth-2-yl                                                                          blue (510)                          31   4-[N-methyl-N-(β-sulfatoethyl-                                                           3-    6-(β-sulfatoethylsulfonyl)-                                                             navy                                     sulfonyl)]-amino-phenyl                                                                             1-sulfo-naphth-2-yl                                                                          blue (514)                          32   4-[N-methyl-N-(β-sulfatoethyl-                                                           3-    8-(β-sulfatoethylsulfonyl)-                                                             navy                                     sulfonyl)]-amino-phenyl                                                                             naphth-2-yl    blue                                33   3-[N-methyl-N-(β-sulfatoethyl-                                                           3-    8-(β-sulfatoethylsulfonyl)-                                                             navy                                     sulfonyl)]-amino-phenyl                                                                             naphth-2-yl    blue                                34   3-[N-methyl-N-(β-sulfatoethyl-                                                           3-    8-vinylsulfonyl-6-sulfo-                                                                     navy                                     sulfonyl)]-amino-phenyl                                                                             naphth-2-yl    blue                                35   4-(N-ethyl-N-(β-sulfatoethyl-                                                            3-    8-vinylsulfonyl-6-sulfo-                                                                     navy                                     sulfonyl)]-amino-phenyl                                                                             naphth-2-yl    blue                                36   4-(N-ethyl-N-(β-sulfatoethyl-                                                            3-    6-vinylsulfonyl-8-sulfo-                                                                     navy                                     sulfonyl)]-amino-phenyl                                                                             naphth-2-yl    blue                                37   3-[N-methyl-N-(β-sulfatoethyl-                                                           3-    8-vinylsulfonyl-6-sulfo-                                                                     navy                                     sulfonyl)]-amino-phenyl                                                                             naphth-2-yl    blue                                38   3-[N-methyl-N-(β-sulfatoethyl-                                                           3-    2-bromo-4-(β-sulfatoethyl-                                                              navy                                     sulfonyl)]-amino-phenyl                                                                             sulfonyl)-phenyl                                                                             blue (612)                          39   4-[N-methyl-N-(β-sulfatoethyl-                                                           3-    2-bromo-4-(β-sulfatoethyl-                                                              navy                                     sulfonyl)]-amino-phenyl                                                                             sulfonyl)-phenyl                                                                             blue (620)                          40   4-[N-methyl-N-(vinylsulfonyl)]-                                                               3-    2-bromo-4-(β-sulfatoethyl-                                                              navy                                     amino-phenyl          sulfonyl)-phenyl                                                                             blue (621)                          41   3-[N-methyl-N-(β-sulfatoethyl-                                                           4-    4-(β-sulfatoethylsulfonyl)-                                                             navy                                     sulfonyl)]-amino-phenyl                                                                             phenyl         blue                                42   4-[N-methyl-N-(β-sulfatoethyl-                                                           4-    4-(β-sulfatoethylsulfonyl)-                                                             navy                                     sulfonyl)]-amino-phenyl                                                                             phenyl         blue                                43   4-[N-methyl-N-(β-sulfatoethyl-                                                           4-    2-bromo-4-(β-sulfatoethyl-                                                              navy                                     sulfonyl)]-amino-phenyl                                                                             sulfonyl)-phenyl                                                                             blue (570)                          44   3-[N-methyl-N-(β-sulfatoethyl-                                                           4-    2-bromo-4-(β-sulfatoethyl-                                                              navy                                     sulfonyl)]-amino-phenyl                                                                             sulfonyl)-phenyl                                                                             blue (566)                          45   3-[N-methyl-N-(β-sulfatoethyl-                                                           4-    2,5-dimethoxy-4-(β-sulfato-                                                             navy                                     sulfonyl)]-amino-phenyl                                                                             ethylsulfonyl)-phenyl                                                                        blue                                46   4-[N-methyl-N-(β-sulfatoethyl-                                                           4-    2,5-dimethoxy-4-(β-sulfato-                                                             navy                                     sulfonyl)]-amino-phenyl                                                                             ethylsulfonyl)-phenyl                                                                        blue                                47   4-[N-methyl-N-(β -sulfatoethyl-                                                          4-    2-sulfo-4-(β-sulfatoethyl-                                                              navy                                     sulfonyl)]-amino-phenyl                                                                             sulfonyl)-phenyl                                                                             blue (576)                          48   3-[N-methyl-N-(β-sulfatoethyl-                                                           4-    2-sulfo-4-(β-sulfatoethyl-                                                              navy                                     sulfonyl)]-amino-phenyl                                                                             sulfonyl)-phenyl                                                                             blue (570)                          49   3-[N-methyl-N-(β-sulfatoethyl-                                                           4-    6-(β-sulfatoethylsulfonyl)-                                                             navy                                     sulfonyl)]-amino-phenyl                                                                             1-sulfo-naphth-2-yl                                                                          blue                                50   4-[N-methyl-N-(β-sulfatoethyl-                                                           4-    6-(β-sulfatoethylsulfonyl)-                                                             navy                                     sulfonyl)]-amino-phenyl                                                                             1-sulfo-naphth-2-yl                                                                          blue                                51   4-vinylsulfonyl-phenyl                                                                        3-    4-[N-methyl-N-(β-sulfato-                                                               navy                                                           ethylsulfonyl)]-amino-phenyl                                                                 blue                                52   3-(β-sulfatoethylsulfonyl)-                                                              3-    4-[N-methyl-N-(β-sulfato-                                                               navy                                     phenyl                ethylsulfonyl)]-amino-phenyl                                                                 blue                                53   3-vinylsulfonyl-phenyl                                                                        3-    4-[N-methyl-N-(β-sulfato-                                                               navy                                                           ethylsulfonyl)]-amino-phenyl                                                                 blue                                54   2-methoxy-5-(β-sulfatoethyl-                                                             3-    4-[N-methyl-N-(β-sulfato-                                                               navy                                     sulfonyl)-phenyl      ethylsulfonyl)]-amino-phenyl                                                                 blue                                55   2-sulfo-4-vinylsulfonyl-phenyl                                                                3-    4-[N-methyl-N-(β-sulfato-                                                               navy                                                           ethylsulfonyl)]-amino-phenyl                                                                 blue                                56   2-sulfo-5-vinylsulfonyl-phenyl                                                                3-    4-[N-methyl-N-(β-sulfato-                                                               navy                                                           ethylsulfonyl)]-amino-phenyl                                                                 blue                                57   6-(β-sulfatoethylsulfonyl)-                                                              3-    4-[N-methyl-N-(β-sulfato-                                                               navy                                     naphth-2-yl           ethylsulfonyl)]-amino-phenyl                                                                 blue                                58   6-(β-sulfatoethylsulfonyl)-                                                              3-    4-[N-methyl-N-(β-sulfato-                                                               navy                                     1-sulfo-naphth-2-yl   ethylsulfonyl)]-amino-phenyl                                                                 blue                                59   4-(β-sulfatoethylsulfonyl)-                                                              3-    3-[N-methyl-N-(β-sulfato-                                                               navy                                     phenyl                ethylsulfonyl)]-amino-phenyl                                                                 blue                                60   4-vinylsulfonyl-phenyl                                                                        3-    3-[N-methyl-N-(β-sulfato-                                                               navy                                                           ethylsulfonyl)]-amino-phenyl                                                                 blue (590)                          61   2-methoxy-5-(β-sulfatoethyl-                                                             3-    3-[N-methyl-N-(β-sulfato-                                                               navy                                     sulfonyl)-phenyl      ethylsulfonyl)]-amino-phenyl                                                                 blue (594)                          62   2-sulfo-5-(β-sulfatoethyl-                                                               3-    3-[N-methyl-N-(β-sulfato-                                                               navy                                     sulfonyl)-phenyl      ethylsulfonyl)]-amino-phenyl                                                                 blue                                63   4-sulfo-5-(β-sulfatoethyl-                                                               3-    3-[N-methyl-N-(β-sulfato-                                                               navy                                     sulfonyl)-phenyl      ethylsulfonyl)]-amino-phenyl                                                                 blue                                64   6-(β-sulfatoethylsulfonyl)-                                                              3-    3-[N-methyl-N-(β-sulfato-                                                               navy                                     naphth-2-yl           ethylsulfonyl)]-amino-phenyl                                                                 blue                                65   6-(β-sulfatoethylsulfonyl)-                                                              3-    3-[N-methyl-N-(β-sulfato-                                                               navy                                     1-sulfo-naphth-2-yl   ethylsulfonyl)]-amino-phenyl                                                                 blue                                66   3-[N-methyl-N-(β-sulfatoethyl-                                                           3-    3-[N-methyl-N-(β-sulfato-                                                               navy                                     sulfonyl)]-amino-phenyl                                                                             ethylsulfonyl)]-amino-phenyl                                                                 blue                                67   3-[N-ethyl-N-(β-sulfatoethyl-                                                            3-    3-[N-methyl-N-(β-sulfato-                                                               navy                                     sulfonyl)]-amino-phenyl                                                                             ethylsulfonyl)]-amino-phenyl                                                                 blue                                68   4-[N-methyl-N-(β-sulfatoethyl-                                                           3-    3-[N-methyl-N-(β-sulfato-                                                               navy                                     sulfonyl)]-amino-phenyl                                                                             ethylsulfonyl)]-amino-phenyl                                                                 blue                                69   4-[N-ethyl-N-(β-sulfatoethyl-                                                            3-    3-[N-methyl-N-(β-sulfato-                                                               navy                                     sulfonyl)]-amino-phenyl                                                                             ethylsulfonyl)]-amino-phenyl                                                                 blue                                70   4-[N-ethyl-N-(β-sulfatoethyl-                                                            3-    4-[N-methyl-N-(β-sulfato-                                                               navy                                     sulfonyl)]-amino-phenyl                                                                             ethylsulfonyl)]-amino-phenyl                                                                 blue (612)                          71   4-[N-methyl-N-(β-sulfatoethyl-                                                           3-    4-[N-methyl-N-(β-sulfato-                                                               navy                                     sulfonyl)]-amino-phenyl                                                                             ethylsulfonyl)]-amino-phenyl                                                                 blue (610)                          72   3-[N-methyl-N-(β-sulfatoethyl-                                                           3-    4-[N-methyl-N-(β-sulfato-                                                               navy                                     sulfonyl)]-amino-phenyl                                                                             ethylsulfonyl)]-amino-phenyl                                                                 blue                                73   3-[N-ethyl-N-(β-sulfatoethyl-                                                            3-    4-[N-methyl-N-(β-sulfato-                                                               navy                                     sulfonyl)]-amino-phenyl                                                                             ethylsulfonyl)]-amino-phenyl                                                                 blue                                74   4-[N-methyl-N-(vinylsulfonyl)]-                                                               3-    4-[N-methyl-N-(vinyl-                                                                        navy                                     amino-phenyl          sulfonyl)]-amino-phenyl                                                                      blue (614)                          75   3-[N-methyl-N-(vinylsulfonyl)]-                                                               3-    3-[N-methyl-N-(vinyl-                                                                        navy                                     amino-phenyl          sulfonyl)]-amino-phenyl                                                                      blue                                76   2-sulfo-3-[N-methyl-N-(vinyl-                                                                 3-    2-sulfo-3-[N-methyl-N-                                                                       navy                                     sulfonyl)]-amino-phenyl                                                                             (vinylsulfonyl)]-amino-phenyl                                                                blue                                77   4-(β-sulfatoethylsulfonylmethyl)-                                                        3-    4-[N-methyl-N-(β-sulfato-                                                               navy                                     amino-phenyl          ethylsulfonyl)]-amino-phenyl                                                                 blue (610)                          78   3-(β-sulfatoethylsulfonylmethyl)-                                                        3-    4-[N-methyl-N-(β-sulfato-                                                               navy                                     amino-phenyl          ethylsulfonyl)]-amino-phenyl                                                                 blue                                79   3-(β-sulfatoethylsulfonylmethyl)-                                                        3-    3-[N-methyl-N-(β-sulfato-                                                               navy                                     amino-phenyl          ethylsulfonyl)]-amino-phenyl                                                                 blue                                80   4-(β-sulfatoethylsulfonylmethyl)-                                                        3-    3-[N-methyl-N-(β-sulfato-                                                               navy                                     amino-phenyl          ethylsulfonyl)]-amino-phenyl                                                                 blue                                81   4-[N-methyl-N-(β-sulfatoethyl-                                                           3-    4-(β-sulfatoethylsulfonyl-                                                              navy                                     sulfonyl)]-aminophenyl                                                                              methyl)-amino-phenyl                                                                         blue (602)                          82   4-[N-methyl-N-(β-sulfatoethyl-                                                           3-    3-(β-sulfatoethylsulfonyl-                                                              navy                                     sulfonyl)]-aminophenyl                                                                              methyl)-amino-phenyl                                                                         blue (598)                          __________________________________________________________________________

We claim:
 1. A disazo compound corresponding to the formula ( 1)##STR10## in which: D* is phenylene, which is unsubstituted orsubstituted by 1 or 2 substituents from the group consisting of alkylhaving 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, chlorine,bromine, sulfo and carboxy, or is naphthylene, which is unsubstituted orsubstituted by 1 or 2 sulfo groups;D is meta- or para-phenylene; A is adirect bond or methylene; R is alkyl having from 1 to 4 carbon atoms,which is unsubstituted or substituted by cyano or carbalkoxy of 2 to 5carbons; Y¹ and Y² each is vinyl, β-chloroethyl or β-sulfatoethyl, andY¹ and Y² have meanings which are identical to or different from oneanother; and M is hydrogen or an alkali metal.
 2. A compound as claimedin claim 1, corresponding to the formula (1a) ##STR11##
 3. A compound asclaimed in claim 1, corresponding to the formula (1b) ##STR12##
 4. Acompound as claimed in claim 1, in which D* is meta- or para-phenylenewhich is unsubstituted or substituted by 1 or 2 substituents chosen fromthe following group of substituents: 2 methoxy, 1 ethoxy, 1 methyl, 2chloro and 1 sulfo.
 5. A compound as claimed in claim 1, in which D* isnaphthylene which contains the azo group in the 2-position and isunsubstituted or substituted by a sulfo group.
 6. A compound as claimedin claim 1, in which D* is para-phenylene and A is a direct bond.
 7. Acompound as claimed in claim 1, in which R is methyl.
 8. A compound asclaimed in claim 1, in which Y¹ and Y² are both β-sulfatoethyl.
 9. Acompound as claimed in claim 2, in which D* is meta- or para-phenylenewhich is unsubstituted or substituted by 1 or 2 substituents chosen fromthe following group of substituents: 2 methoxy, 1 ethoxy, 1 methyl, 2chloro and 1 sulfo.
 10. A compound as claimed in claim 2, in which D* isnaphthylene, which contains the azo group in the 2-position and isunsubstituted or substituted by a sulfo group.
 11. A compound as claimedin claim 2, in which D* is para-phenylene and A is a direct bond.
 12. Acompound as claimed in claim 3, in which D* is meta- or para-phenylenewhich is unsubstituted or substituted by 1 or 2 substituents chosen fromthe following group of substituents: 2 methoxy, 1 ethoxy, 1 methyl, 2chloro and 1 sulfo.
 13. A compound as claimed in claim 3, in which D* isnaphthylene, which contains the azo group in the 2-position and isunsubstituted or substituted by a sulfo group.
 14. A compound as claimedin claim 3, in which D* is para-phenylene and A is a direct bond.
 15. Acompound as claimed in claim 2, in which R is methyl.
 16. A compound asclaimed in claim 3, in which R is methyl.
 17. A disazo compound asclaimed in claim 1, of the formula ##STR13##
 18. A disazo compound asclaimed in claim 1, of the formula ##STR14##